New poly(meth)acrylate compositions containing amide acetals

ABSTRACT

The present invention relates to novel poly(meth)acrylate compositions formed by polymerization of (meth)acrylate amide acetals.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application60/615,361, filed Sep. 30, 2004.

FIELD OF THE INVENTION

The present invention relates to novel poly(meth)acrylate compositionsformed by polymerization of (meth)acrylate amide acetals.

BACKGROUND OF THE INVENTION

Amide acetals have been used for example in copolymerization withpolyisocyanates as disclosed in U.S. Pat. No. 4,721,767. Cross-linkedamide acetal based coating compositions dry and cure rapidly without thepotential problems created by VOC emissions. Such coatings can be veryuseful, for example, in the automotive coatings industry.

Co-owned and co-pending U.S. patent Publication 2005-007461 describespolymeric compositions containing amide acetal groups, which arecrosslinked by hydrolyzing the amide acetal groups, and subsequentlyreacting the hydroxyl groups and/or the amine functions that are formedto crosslink the composition.

Co-owned and co-pending U.S. patent application Ser. No. 10/960656describes a catalytic process for making amide acetals from nitrites anddiethanolamines.

Co-owned and co-pending U.S. patent application 60/615362 describesnovel (meth)acrylate amide acetals and processes to make them.

SUMMARY OF THE INVENTION

The present invention relates to a composition, comprising:

wherein R₄₂-R₄₉ independently represent a hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may eachhave one or more substituents selected from the groups consisting ofhalo, alkoxy, imino, dialkylamino;

R₄₁ is (CR₅₀R₅₁)_(n), wherein R₅₀ and R₅₁ are each independentlyrepresent a hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ alkenyl, C₁-C₂₀ alkynyl,C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀ aralkyl group;

n is 1-10;

R₅₂ is hydrogen or methyl;

R′ is hydrogen or methyl;

R″ is C₁-C₃₀ alkyl or C₃-C₃₀ aromatic; and

N, M and P represent percentages of 100% such that N+M+P=100%.

The present invention further relates to a process to make polymerscomprising (meth)acrylate amide acetals, comprising reacting a(meth)acrylate amide acetal of the formula

wherein R₄₂-R₄₉ independently represent a hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may eachhave one or more substituents selected from the groups consisting ofhalo, alkoxy, imino, and dialkylamino;

R₄₁ is (CR₅₀R₅₁)_(n), wherein R₅₀ and R₅₁ are each independentlyrepresent a hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ alkenyl, C₁-C₂₀ alkynyl,C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀ aralkyl group

R₅₂ is hydrogen or methyl; and

n is 1 to 10.

The present invention further relates to a process wherein the(meth)acrylate amide acetal is reacted with one or more monomersselected from the group consisting ofR′—C(CH₂)—C(O)—OR″where R′ is hydrogen or methyl, and R″ is C₁-C₃₀ alkyl groups oraromatic groups; styrene and substituted styrenes.

The invention further relates to a process wherein the product isrepresented by the formula

wherein R₄₂-R₄₉ independently represent a hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may eachhave one or more substituents selected from the groups consisting ofhalo, alkoxy, imino, and dialkylamino;

R₄₁ is (CR₅₀R₅₁)n, wherein R₅₀ and R₅₁ are each independently representa hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl,C₁-C₂₀ alkyl ester, or C₁-C₂₀ aralkyl group

n is 1 to 10;

R₅₂ is hydrogen or methyl;

R′ is hydrogen or methyl;

R″ is C₁-C₃₀ alkyl or C₃-C₃₀ aromatic; and

N, M and P represent percentages of 100% such that N+M+P=100%.

The polymers of the present invention may be made by polymer formationprocesses including free radical polymerization and group transferpolymerization.

DETAILS OF THE INVENTION

The present invention relates to the preparation of poly(meth)acrylateamide acetals. The preparation of the (meth)acrylate amide acetals isdescribed in co-owned and co-pending U.S. patent application 60/615362,hereby incorporated by reference in its entirety.

As described in U.S. patent application 60/615362, amide acetals havethe general formula

General processes for producing amide acetals are disclosed in co-ownedand co-pending U.S. patent Publication 2005-007461 and application Ser.No. 10/960656. As disclosed in these applications, amide acetals canalso be represented by the formula

wherein R₄₂-R₄₉ independently represent a hydrogen, C₁-C20 alkyl. C₁-C₂₀alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may eachhave one or more substituents selected from the groups consisting ofhalo, alkoxy, imino, and dialkylamino; and R₄₁ is (CR₅₀R₅₁)_(n), whereinR₅₀ and R₅₁ are each independently represent a hydrogen, C₁-C₂₀ alkyl,C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀ aralkylgroup, where n is 1-10. It is more typical that R₄₂-R₄₉ eachindependently represent hydrogen and C₁-C₁₀ alkyl groups. This amideacetal is used to produce (meth)acrylate amide acetals by any of severalmethods, including transesterification, reaction with an acid halide or(meth)acrylate anhydride in the presence of a base.

With transesterification, the amide acetal would react with an estersuch asCH₂═C(R)—C(O)—OR′where R is hydrogen or methyl and R′ is C₁-C₂₀ alkyl. Reaction with anacid halide, such asCH₂═C(R)—C(O)—Xor a (meth)acrylate anhydrideCH₂═C(R)—C(O)—O—C(O)—C(R)═CH₂where each R is independently hydrogen or methyl and X is a halogen suchas Cl or Br, in the presence of a base (e.g., triethylamine, pyridine)also gives the desired end-product. The formula for these (meth)acrylateamide acetals thus formed is

where R₅₂ is either hydrogen or methyl.

Generally, for a randomly dispersed polymer, the reactants are addedtogether with a common solvent, such as ethyl acetate, butyl acetate,xylenes, toluene, propylene glycol monomethyl ether acetate. Thissolution can then be fed concurrently with a catalyst solution, usuallyan organic peroxide, to a reactor, under nitrogen, stirring withadditional solvent, at the appropriate temperature. For appropriateorganic peroxides, see Elf Atochem “Organic Peroxides”, ProductBulletin, Philadelphia, Pa.

The (meth)acrylate amide acetals are then reacted with other monomers toform oligomers and polymers. By polymers herein are meant those entitieswith number average molecular weight from about 100 to about 100,000.Preferably, the number average molecular weight of the polymers is fromabout 100 to about 10000. By oligomers herein is meant those polymerswhich have a number average molecular weight less than about 3000.

While the (meth)acrylate amide acetals can be reacted with a number ofmonomers, particularly useful ones include those represented by theformulaR′—C(CH₂)—C(O)—OR″where R′ is hydrogen or methyl, and R″ is C₁-C₃₀ alkyl groups oraromatic groups (e.g., phenyl). Additionally, monomers such as styrene

and substituted styrenes such as alpha-methyl styrene, can be reactedwith the (meth)acrylate amide acetals.

The polymers of the present invention can be formed by any convenientprocess. As will be known by those skilled in the art, appropriatesolvents, catalysts, initiators and the like will need to be employed toform the desired end products. One process that may be employed is afree radical process, which will provide polymers of random structures;i.e., the monomers which are reacted together will form random polymers.Another process commonly used for polymerization is group transferpolymerization, which will provide designed polymer structures. See, forinstance, D. Y. Sogah, et al., Macromolecules (1987), 20(7), 1473-88.Still another process that is useful is cobalt chain transferpolymerization, as described in U.S. Pat. No. 5,587,431.

When the monomers described above react to form polymers, their generalstructure will be

where N+M+P=100%. Therefore, depending on the amounts of monomers added,the resulting polymer can be homopolymeric (i.e., N=100%, and M and Pare each 0%) or heteropolymeric (when at least 2 of N, M and P are not0%.

The materials made by the processes disclosed are novel, and may be usedto produce novel coatings.

These and other features and advantages of the present invention will bemore readily understood, by those of ordinary skill in the art, from areading of the following detailed description. It is to be appreciatedthose certain features of the invention, which are, for clarity,described above and below in the context of separate embodiments, mayalso be provided in combination in a single embodiment. Conversely,various features of the invention that are, for brevity, described inthe context of a single embodiment, may also be provided separately orin any sub-combination. In addition, references in the singular may alsoinclude the plural (for example, “a” and “an” may refer to one, or oneor more) unless the context specifically states otherwise.

The use of numerical values in the various ranges specified in thisapplication, unless expressly indicated otherwise, are stated asapproximations as though the minimum and maximum values within thestated ranges were both preceded by the word “about.” In this mannerslight variations above and below the stated ranges can be used toachieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum values.

Unless otherwise stated, all chemicals and reagents were used asreceived from Aldrich Chemical Co., Milwaukee, Wis.

EXAMPLES Example 1

In a dry flask styrene (90.36 g), methyl methacrylate (120.49 g),isobornyl methacrylate (280.16 g), 2-methyl-acrylic acid2,6-dimethyl-tetrahydro-oxazolo[2,3-b]oxazol-7a-ylmethylester (111.63g)—monomer solution. In a separate dry flask butyl acetate (59.55 g) andVazo 67 (14.95 g) were added—catalyst solution.

To a dried flask equipped with a mechanical stirrer, a reflux condenserand under nitrogen was butyl acetate (178.89 g). This solvent was thenheated to 100° C. To the stirred solvent maintained at 100° C. wereadded concurrently the above monomer solution at a rate of 3.31 g/min(addition over ˜3 hours) and the above catalyst solution at a rate of0.31 g/min (addition over ˜4 hours). The polymerized solution was heldat 100° C. for 30 minutes after completion of the catalyst solution andthen cooled to room temperature. GPC analyses of the resulting polymershowed the polymer to contain very little residual monomers, havingbimodal distribution, with Mn=9344 and Mw=20651.

Example 2

In a dry flask styrene (59.60 g), methyl methacrylate (79.3 g),isobornyl methacrylate (167.5 g), 2-methyl-acrylic acid5-(dimethyl-tetrahydro-oxazolo[2,3-b]oxazol-7a-yl)-pentyl ester(90.8 g)and butyl acetate were mixed—monomer solution. In a separate dry flaskbutyl acetate (88.53 g) and Vazo 67 (10.82 g) were added—catalystsolution.

To a dried flask equipped with a mechanical stirrer, a reflux condenserand under nitrogen was butyl acetate (118.1 g). This solvent was thenheated to 100° C. To the stirred solvent maintained at 100° C. wereadded concurrently the above monomer solution at a rate of 3.31 g/min(addition over ˜3 hours) and the above catalyst solution at a rate of0.31 g/min (addition over ˜4 hours). The polymerized solution was heldat 100° C. for 30 minutes after completion of the catalyst solution andthen cooled to room temperature. An additiional 103 g of butyl acetatewas added. GPC analyses of the resulting polymer showed the polymer tocontain almost no residual residual monomers, with Mn=6255 and Mw=13049,PD=2.08.

1. A composition, comprising:

wherein R₄₂-R₄₉ independently represent a hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may eachhave one or more substituents selected from the groups consisting ofhalo, alkoxy, imino, and dialkylamino; R₄₁ is (CR₅₀R₅₁)_(n), wherein R₅₀and R₅₁ are each independently represent a hydrogen, C₁-C₂₀ alkyl,C₁-C₂₀ alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, orC₁-C₂₀ aralkyl group; n is 1 to 10; R₅₂ is hydrogen or methyl; R′ ishydrogen or methyl; R″ is C₁-C₃₀ alkyl or C₃-C₃₀ aromatic; and N, M andP represent percentages of 100% such that N+M+P=100%.
 2. A process tomake polymers comprising (meth)acrylate amide acetals, comprisingreacting a (meth)acrylate amide acetal of the formula

wherein R₄₂-R₄₉ independently represent a hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may eachhave one or more substituents selected from the groups consisting ofhalo, alkoxy, imino, and dialkylamino; R₄₁ is (CR₅₀R₅₁)_(n), wherein R₅₀and R₅₁ are each independently represent a hydrogen, C₁-C₂₀ alkyl,C₁-C₂₀ alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, orC₁-C₂₀ aralkyl group R₅₂ is hydrogen or methyl; and n is 1-10.
 3. Theprocess of claim 2, wherein the (meth)acrylate amide acetal is reactedwith one or more monomers selected from the group consisting ofR′—C(CH₂)—C(O)—OR″ where R′ is hydrogen or methyl, and R″ is C₁-C₃₀alkyl groups or aromatic groups; styrene and substituted styrenes. 4.The process of claim 3, wherein the product is represented by theformula

wherein R₄₂-R₄₉ independently represent a hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, or C₁-C₂₀aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may eachhave one or more substituents selected from the groups consisting ofhalo, alkoxy, imino, and dialkylamino; R₄₁ is (CR₅₀R₅₁)_(n), wherein R₅₀and R₅₁ are each independently represent a hydrogen, C₁-C₂₀ alkyl,C₁-C₂₀ alkenyl, C₁-C₂₀ alkynyl, C₁-C₂₀ aryl, C₁-C₂₀ alkyl ester, orC₁-C₂₀ aralkyl group; n is 1-10; R₅₂ is hydrogen or methyl; R′ ishydrogen or methyl; R″ is C₁-C₃₀ alkyl or C₃-C₃₀ aromatic; and N, M andP represent percentages of 100% such that N+M+P=100%.
 5. The process ofclaim 4, wherein said process is a free radical process.
 6. The processof claim 4, wherein said process is a group transfer polymerizationprocess.
 7. The process of claim 4, wherein said process is a cobaltchain transfer polymerization process.